JPS6369803A - Polymerization of olefin - Google Patents

Abstract

PURPOSE:To produce a polyolefin in high yield, by polymerizing an olefin using a transition metal catalyst prepared by using a carrier comprising a halogenated Mg produced by a specific method and supporting halogenated Ti on the carrier using a specific method. CONSTITUTION:A carrier comprising a halogenated Mg of formula MgX<1>X<2> produced by the reaction of a Grignard reagent of formula R<1>MgX<1> (R<1> is hydrocarbon residue; X<1> is halogen) with a halogenated hydrocarbon of formula R<2>X<2> (R<2> is hydrocarbon residue; X<2> is halogen) is made to contact with an oxygen-containing organic compound selected from esters, orthoesters and alkoxysilanes (preferably methyl acrylate, methyl benzoate, etc., at an amount of 0.05-5mol per 1mol of MgX<1>X<2>) in the presence of a halogenated Ti excess to said organic compound (preferably 5-1,000mol of the Ti compound based on 1mol of the organic compound). The obtained transition metal catalyst is used in combination with an organometallic compound of the group 1-3 metal of the periodic table (e.g. organic Al compound). An olefin is polymerized in the presence of the obtained catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for polymerizing olefins. Specifically, the present invention relates to a method of polymerizing olefins using magnesium halide obtained by a specific method as a carrier and a transition metal catalyst obtained by supporting titanium halide by a specific method.

[Prior Art] In the polymerization of olefins, synthesis of polyolefins using a transition metal catalyst consisting of a titanium halide supported on a carrier such as magnesium halide and a catalyst consisting of an organometallic compound was disclosed in Japanese Patent Publication No. 12105/1983. Since its disclosure, various improved methods have been proposed.

In particular, magnesium halide is solubilized in a hydrocarbon solvent using an electron-donating compound such as alcohol, and a magnesium halide carrier is produced using a precipitant such as titanium tetrachloride or silicon tetrachloride, and titanium halide is supported on the magnesium halide carrier. catalysts (for example, JP-A-59-117508, JP-A-59-117508,
8-83006, 56-11908, etc.) gives extremely excellent results.

However, the olefin polymerization method using the catalyst described above requires a large amount of precipitant to produce the catalyst, and it is also necessary to carry out the operation of supporting titanium halide repeatedly using a large amount of titanium halide. There was a problem with the production of the catalyst.

[Problems to be Solved by the Invention] As a result of intensive research into a method for polymerizing olefins using a catalyst that does not have the production drawbacks of conventional transition metal catalysts, the present inventors have found that /\magnesium rogenide obtained by a specific method. We have completed the present invention by discovering that the above problems can be solved by using a catalyst in which titanium chloride is supported in a specific manner using a carrier, and that extremely excellent results can be obtained in the polymerization reaction.

[Means for Solving the Problems] That is, the present invention provides a solution having the general formula R1MgXI (wherein 1li
1 is a hydrocarbon residue, and XI is a halogen atom. ) and a Grignard reagent represented by the general formula R2X2 (wherein, R2 is a hydrocarbon residue, and x2 is a /S logen atom).

) MgXI This olefin polymerization method is characterized by using a transition metal catalyst obtained by further contacting with titanium halide and an organometallic compound of a metal from Group 1 to Group 3 of the periodic table.

The present invention will be explained in detail below.

The catalyst used in the present invention is a carrier of MgXlX2 (wherein, Xl and x2 are each independently a halogen atom).
It has important characteristics in its production and can be obtained as follows.

First, R1MgX' (where R1 is a hydrocarbon residue,
is a halogen atom. The Grignard reagent represented by ) can be produced by a known method, and is generally)
It is produced by reacting a halogenated hydrocarbon represented by XI with metallic magnesium. Here, the hydrocarbon residue may be of any kind, such as aliphatic, alicyclic, or aromatic hydrocarbon residues, and is not particularly limited, but it is common to use one with a carbon number of about 1 to 20. It is. Examples of xl include iodine, bromine, and chlorine.

The halogenated hydrocarbon represented by R2X2 (in the formula, R2 is a hydrocarbon residue, and x2 is a halogen atom), which is one component used in the production of MgXI X2, is the one used in the production of the Grignard reagent. Although there are no particular limitations, bromine or iodine can be used as the halogen atom of the halogenated hydrocarbon when producing the Grignard reagent.
When chlorine is used as x2 in R2X2, MgXI X2 containing a halogen atom can be easily obtained in good yield.

In the present invention, MgXI obtained in the above reaction is then
X' is contacted with an oxygen-containing organic compound selected from esters, orthoesters, and alkoxy silicones in the presence of titanium halide in excess of the oxygen-containing organic compound. In this case, pentane, hexane, heptane, decane, nonane, benzene, toluene, xylene, ethylbenzene, methylene dichloride, ethylene dichloride, 1,1-dichloroethane,
It can also be carried out by diluting with an inert medium such as trichloroethane, and MgXI It is common to carry out a contact treatment by adding the oxygen-containing organic compound to MgXlX2, and the ratio of the oxygen-containing organic compound to MgXlX2 is 0.001 to 10 times by mole, usually 0.05 to 5 times by mole.

Specifically, the oxygen-containing organic compounds include unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate, methyl benzoate, ethyl benzoate, methyl toluate, ethyl toluate, Aromatic carboxylic acid esters such as methyl anisate, ethyl anisate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, methyl isophthalate, ethyl isophthalate, methyl terephthalate, and ethyl terephthalate, methyl orthoformate , ethyl orthoacetate, methyl orthoacetate, ethyl orthoacetate, methyl orthobenzoate, ethyl orthobenzoate, orthoesters, orthosilicate esters, dimethyldimethoxysilane, diethyljethoxysilane, triethylethoxysilane, ethyltriethoxysilane, methyl Examples include alkoxysilicon such as trimethoxysilane and phenyltrimethoxysilane.

As the titanium halide, it is preferable to use a tetravalent titanium halide containing one or more halogen atoms per titanium and containing or not containing an alkoxy group, and titanium tetrachloride is particularly preferably used.

The titanium halide is used in excess of the oxygen-containing organic compound, that is, at least 5 moles or more, preferably at least 5 moles or more.
It is carried out under conditions of about twice the molar ratio.

In this case, if the amount of titanium halide used is small, not only will the activity of the transition metal catalyst obtained be insufficient, but also the stereoregularity of the polymer obtained when used in the stereoregular polymerization of α-olefins will deteriorate. Contact treatment temperature is room temperature ~ 200℃
It is generally carried out at ℃.

In the present invention, the liquid phase is then removed by decantation, filtration, etc., and the solid content is then further treated with the same titanium halide as described above. This contact treatment is performed in the presence or absence of the above-mentioned inert hydrocarbon, and the contact temperature is from room temperature to 200°C, usually from 50 to 150°C.

After the contact treatment, excess titanium halide is removed by evaporation or washing with an inert hydrocarbon to obtain a transition metal catalyst.

Examples of the organometallic compounds of metals from Groups 1 to 3 of the periodic table used in the present invention include organolithium, organosodium, organomagnesium, organoberyllum, and organoaluminium, among which organoaluminum is preferably used.

Examples of olefins used in the polymerization of the present invention include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, styrene, and vinylnaphthalene. Used for copolymerization with dienes, etc.

In the present invention, olefin polymerization is carried out using a transition metal catalyst comprising a titanium halide supported on the magnesium halide carrier obtained as described above, and a transition metal catalyst of groups 1 to 3 of the periodic table.
Other than using a catalyst consisting of an organometallic compound of group metal, conventional olefin polymerization methods can be applied, such as solution polymerization using a solvent, bulk polymerization using the olefin itself as a medium, or gas phase polymerization that does not substantially contain a solvent. Possible.

[Example] The present invention will be further explained below with reference to Examples.

Example 1 7.4 g of magnesium in a 300 mJ1 round bottom flask,
Add 20ml of diethyl ether and add 50g of cyclohexane bromide and 50+* of diethyl ether while refluxing the ether.
A mixture of u was added dropwise over 2 hours. Thereafter, the mixture was further stirred under reflux for 1 hour to prepare an ethyl ether solution of C6H++MgBr.

Allyl chloride 24 was then added under reflux of ethyl ether.
50+sJ1 was added dropwise over 3 hours, and the mixture was further stirred under reflux for 4 hours.

Then, it was filtered at room temperature, and the solid content was washed with ethyl ether and dried with a nitrogen stream to obtain 41 g of solid content. The solid content obtained was MgBr with a ratio of Mg:CI:Br of approximately 1:1:1.
It was C1.

- Put 10g of the solid content in a 200+mJl round bottom flask, add 1.5ml of diisobutyl phthalate, 7ml of titanium tetrachloride, and 107ml of toluene. Stir at 2oC for 1 hour, then stand to separate. Clear was removed. Next, 100 tJL of titanium tetrachloride was added, and the mixture was stirred at 130°C for 1 hour, allowed to stand, and the supernatant was removed. The resulting solid content was washed 9 times with n-hexane to obtain a transition metal catalyst. The analysis results showed that it contained 3.2wtX titanium.

Ethylene was polymerized using the transition metal catalyst obtained in the above operation and triethylaluminum as an organometallic compound catalyst. Add 1 part of n-hebutane, 20 mg of the above transition metal catalyst, and 0.5 parts of triethyl aluminum to an autoclave with an internal volume of 2 volumes, add hydrogen to 2 kg/am2 gauge, and add ethylene to 6 kg/cm2 gauge. After adding, the temperature was raised to 75℃ and 10 kg/cm2
2 at 75℃ while adding ethylene to the gauge.
Polymerized for hours. Thereafter, the mixture was cooled, unreacted ethylene was purged, and then filtered to obtain polyethylene powder. The dry weight was 690 g. This corresponds to (34500 g/g per transition metal catalyst). The intrinsic viscosity of this powder is 2.75 (measured with a tetralin solution at 135°C), the bulk specific gravity is 0.40 g/ts, and the particle size is 0.3% fine powder of 200 mesh or less, 10 mesh or more.
- The coarse particles were 0%.

Example 2 Propylene was polymerized using the transition metal catalyst obtained in Example 1 and triethylaluminum. 5 sentences of autoclave L Transition metal catalyst 30 mg, diethylaluminum chloride 0.128 mJl, P-1 methyl ruylate 0.0
Add 8 mJl, 0.12 mJl of triethylaluminum, add 1.5 kg of propylene and 3.2 NL of hydrogen, 75
The temperature was raised to 75°C and polymerization was carried out for 2 hours. After 2 hours, unreacted propylene was purged, and the polypropylene was taken out, dried and weighed, and 720 g of polypropylene was obtained. This corresponds to (IJ per transition metal catalyst 24000 g/g). The intrinsic viscosity of this polymer is 1.78, the bulk specific gravity is 0.39 g/ml, and the residual ratio after extraction with n-heptane is 96.
9% (extracted using a Soxhlet extractor with boiling!! 1 tn-hebutane for 6 hours, calculated as weight after extraction ÷ weight before extraction x lOO).

Example 3 840 g of polypropylene was obtained in the same manner as in Example 2, except that 30 mg of the transition metal catalyst obtained in Example 1, 0.03 ml of trimethoxyphenylsilane, and 0.15 tin of triethylaluminum were used. The obtained polypropylene had an intrinsic viscosity of 1.65 and a bulk specific gravity of 0.41 g.
/tan, Buddha 11n-heptane extraction residual rate 97.6wt
%Met.

Comparative Example 1 Titanium tetrachloride 50+a was treated with diisobutyl phthalate.
In addition to JL, 50+wu of toluene (therefore, the total amount of toluene is 60I11!;L) and 80% of the contact treatment.
The same procedure as in Example 3 was carried out except that the transition metal catalyst obtained was used. 420 g of polypropylene was obtained, and the intrinsic viscosity of the polypropylene was 1.
．． 88, bulk specific gravity 0.38 g/ran, boiling n-heptane extraction residual rate 9B, 2 wt%.

Example 4.5 1.5 ethyl orthoacetate instead of diisobutyl phthalate
+wJL (Example 4) Tetraethoxysilane 1.5a
The same procedure as Example 1 was carried out except that n (Example 5) was used, and 520 g of polyethylene, (intrinsic viscosity number 3
．． 545 g (intrinsic viscosity number 2.85, bulk specific gravity 0.39 g/ml) was obtained.

As is clear from "Advantageous Effects of the Invention 1 and 2" above, the present invention solves the drawbacks of conventional catalyst production and makes it possible to polymerize polyolefins with good yield, which is industrially valuable.

[Brief explanation of the drawing]

FIG. 1 is a flowchart regarding the olefin polymerization catalyst used in the present invention.

Claims (1)

[Claims] A Grignard reagent represented by the general formula R^1MgX^1 (wherein R^1 is a hydrocarbon residue and X^1 is a halogen atom) and a general formula R^2X^2 (wherein R^2 is a hydrocarbon residue, and X^2 is a halogen atom.) MgX^1X obtained by reaction with a halogenated hydrocarbon represented by
After contacting ^2 with an oxygen-containing organic compound selected from esters, orthoesters, and alkoxy silicones in the presence of titanium halide in excess of the oxygen-containing organic compound,
A method for polymerizing olefins, which further comprises using a catalyst comprising a transition metal catalyst obtained by contacting with titanium halide and an organometallic compound of a metal from Group 1 to Group 3 of the periodic table.